Enhanced mechanical and thermal strength in mixed enantiomers based supramolecular gel

Mixing supramolecular gels based on enantiomers leads to re-arrangement of gel fibers at the molecular level, which results in more favorable packing and tuneable properties. Bis(urea) compounds tagged with a phenylalanine methyl ester in racemic and enantiopure forms were syn-thesized. Both enantiopure and racemate compounds formed gels in a wide range of solvents and the racemate (1-rac) formed a stronger gel network compared to the enantiomers. The gel (1R+1S) obtained by mixing equimolar amount of enantiomers (1R and 1S) showed enhanced mechanical and thermal stability compared to enantiomers and racemate gels. The preservation of chirality in these compounds was analyzed by circular dichroism and optical rotation measurements. Analysis of the SEM and AFM images revealed that the network in the mixed gel is a combination of enantiomers and racemate fibers, which was further supported by solid state NMR. The analysis of the packing in xerogels by solid state NMR spectra and the existence of twisted-tape morphology in SEM and AFM images confirmed the presence of both self-sorted and co-assembled fibers in mixed gel. The enhanced thermal and mechanical strength may be attributed to the enhanced intermolecular forces between the racemate and enantiomer and the combination of both self-sorted and co-assembled enantiomers in the mixed gel.We thank University of Iceland Research Fund for financial support. D.G. thanks University of Iceland for the Doctoral Research grant and Z.K. thanks University of Ljubljana for the Erasmus exchange program. We thankfully acknowledge Dr. A. Rawal, The Mark Wainwright Analytical Centre, UNSW for solid state NMR studies and Dr. Sigrídur Jónsdóttir, University of Iceland for solution NMR and Mass spectroscopy. P.T. thanks the Australian Research Council for an ARC Centre of Excellence grant (CE140100036) and A.D.M. thanks the National Health and Medical Research Council for a Dementia Development Research Fellowship (APP1106751). L.F. and A.V. thank the FCT (UID/BIO/04469/2013), COMPETE 2020 (POCI-01-0145-FEDER-006684), and Norte2020 Programa Operacional Regional do Norte (BioTecNorte operation, NORTE-01-0145-FEDER-000004) for rheological studies. The rheological study was supported by a STSM Grant from COST Action CM1402 Crystallize.info:eu-repo/semantics/publishedVersio

Smíði og greining á þversameinda gelum með amíð og þvagefna virkni.

Supramolecular gels based on low molecular weight gelators (LMWGs) have witnessed a tremendous growth over last decade due to the emerging potential applications such as dynamic gels, biological applications using gels as cell growth media and also medium to control crystal growth, drug delivery etc. LMWGs are formed by the immobilisation of the solvent molecules in the 3-D network of the gelators via non-covalent interactions such as hydrogen bonding, van der Waals interactions, π−π stacking etc. The structure and properties of the supramolecular gels rely mostly on the geometry of the building blocks and spatial arrangement and nature of the intermolecular non-covalent interactions. The hydrogen bonding motif in gelator plays a crucial role in gel formation. In this BS project, urea motif have been chosen as hydrogen bonding motif since bis-urea motif is well known to form α-tapes, which gel to give a fibre surface. The urea groups in the molecule form strong non-covalent bonds (hydrogen bonds) creating long chains of molecules, which form fibrils that then form the 3D network of the gel. In this context, a series of bis-urea compounds based on amino acids were designed, synthesised and characterised by standard analytical methods. Gelation ability in various solvent and the gel strength have been analysed for all amino acid based compounds synthesised in this BS-project

Solid-State Structural Transformation and Photoluminescence Properties of Supramolecular Coordination Compounds

The combination of strong coordination bonds and hydrogen bonding interactions were used to generate a series of supramolecular coordination materials (SCMs), which was achieved by reacting a bis-pyridyl amide ligand, namely N-(4-pyridyl)nicotinamide (4PNA) with copper(II), zinc(II), and cadmium(II) benzoates. The SCMs were structurally characterized using X-ray diffraction and the key intermolecular interactions were identified via Hirshfeld surface analysis. The role of solvent molecules on the supramolecular architecture was analyzed by synthesizing the SCMs in different solvents/solvent mixtures. A solvent-mediated solid-state structural transformation was observed in copper(II) SCMs and we were able to isolate the intermediate form of the crystal-to-crystal transformation process. The luminescence experiments revealed that complexation enhanced the fluorescence properties of 4PNA in the zinc(II) and cadmium(II) SCMs, but a reverse phenomenon was observed in the copper(II) SCMs. This work demonstrated the tuning of supramolecular assembly in coordination compounds as a function of solvents for generating SCMs with diverse properties